CN121378552B

CN121378552B - A high softening point terpene styrene resin and its preparation method

Info

Publication number: CN121378552B
Application number: CN202511807330.6A
Authority: CN
Inventors: 陈远新; 蔡东明; 王润生; 兰兴燕
Original assignee: Shaoguan Linhe Forestry Products Technology Co ltd
Current assignee: Shaoguan Linhe Forestry Products Technology Co ltd
Priority date: 2025-12-03
Filing date: 2025-12-03
Publication date: 2026-07-24
Anticipated expiration: 2045-12-03
Also published as: CN121378552A

Abstract

The application discloses a high-softening-point terpene styrene resin and a preparation method thereof, belonging to the technical field of high polymer materials, and the technical scheme is that the high-softening-point terpene styrene resin adopts the following technical scheme that the preparation method of the high-softening-point terpene styrene resin comprises the following steps that S1, styrene and myrcene are mixed to obtain a mixed monomer; S2, uniformly mixing butyl acetate and a catalyst at the temperature of less than or equal to 15 ℃, S3, dropwise adding a mixed monomer at the temperature of less than or equal to 10 ℃ in the system of the step S2, and carrying out heat preservation and discharging after the dropwise adding to obtain a polymerization solution, and S4, washing the polymerization solution with hot water to be neutral and then distilling to obtain the terpene styrene resin with high softening point.

Description

Terpene styrene resin with high softening point and preparation method thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a terpene styrene resin with a high softening point and a preparation method thereof.

Background

In the field of high polymer materials, with the continuous development of industry, the demands of various high-performance resin materials are increasing. Polymeric materials play an important role in a wide variety of industries by virtue of their unique physical and chemical properties. For example, in the fields of adhesives, rubber products and the like, the proper resin material can obviously improve the performance and quality of the product. The terpene styrene resin is an important polymer material, and has wide application prospect in various adhesives such as hot melt adhesives, pressure sensitive adhesives, acrylate adhesives and rubber products due to the characteristics of colorless or pale yellow solid appearance, excellent thermal stability, good fluidity, adhesiveness and the like. The adhesive can provide good viscosity for the adhesive, can improve the weather resistance and glossiness of the coating, and has important value in industrial production and daily life.

In the preparation of terpene styrene resins, conventional radical polymerization has been generally employed in the past. Specifically, terpene and styrene monomer are mixed and then caused to undergo polymerization under certain reaction conditions. This method is a relatively common means in the field and is widely used in many production practices. In the reaction process, the basic conditions such as the temperature, the pressure and the like of the reaction are controlled so as to ensure the smooth progress of the reaction. At the same time, some common catalyst is added to accelerate the reaction. In addition, for the treatment of the product after the reaction, conventional separation and purification steps such as water washing, distillation and the like are adopted to obtain a terpene styrene resin product meeting certain quality standards.

However, the terpene styrene resin obtained by the existing preparation method has obvious defects. The highest softening point of the terpene styrene resin prepared by the conventional methods is only 100 ℃, so that the resin cannot be used in the high-temperature field, and the application range of the terpene styrene resin is greatly limited. In some high temperature industrial scenes where the material softening point requirements are high, the existing terpene styrene resins cannot meet the actual requirements.

Disclosure of Invention

In order to solve the problems in the prior art, the application provides the terpene styrene resin with high softening point and the preparation method thereof, and the terpene styrene resin with higher molecular weight and longer molecular chain can be formed by matching styrene, myrcene and butyl acetate, so that the softening point of the terpene styrene resin is more than or equal to 130 ℃.

The first aspect of the invention provides a high softening point terpene styrene resin, which adopts the following technical scheme:

A preparation method of a terpene styrene resin with high softening point comprises the following steps:

s1, mixing styrene and myrcene to obtain a mixed monomer;

s2, uniformly mixing butyl acetate and a catalyst at the temperature of less than or equal to 15 ℃;

s3, dropwise adding the mixed monomer when the temperature of the system in the step S2 is less than or equal to 10 ℃, and carrying out heat preservation and discharging after the dropwise adding to obtain a polymerization solution;

s4, washing the polymerization solution with hot water to be neutral, and then distilling to obtain the terpene styrene resin with high softening point.

In a preferred embodiment, the amount of styrene is 30-40% and the amount of myrcene is 60-70% by weight.

By adopting the technical scheme, the terpene styrene resin with the softening point more than or equal to 130 ℃ can be obtained by copolymerizing the styrene and the myrcene under the butyl acetate, and the terpene styrene resin is characterized in that the myrcene is an open chain monoterpene and contains three carbon-carbon double bonds, wherein two conjugated double bonds are arranged in the two positions, the structural formula has higher chemical reactivity, the chain growth reaction is easier to carry out, when the structure is copolymerized with the styrene, a polymer with higher molecular weight and longer molecular chain can be formed, generally, the higher molecular weight is directly related to the higher softening point, the introduction of the myrcene can form more rigid sequence distribution with the styrene, and the long chain aliphatic structure can form more effective molecular chain entanglement after polymerization, so that the cohesive energy of the polymer is greatly increased, and the heat resistance and the softening point of the polymer are obviously improved.

In addition, when butyl acetate with lower polarity is selected as the solvent, the chain transfer performance of the butyl acetate is better than that of toluene, and the butyl acetate is beneficial to the polymerization of chain extension to obtain the terpene styrene resin with high softening point.

In addition, in the preparation method, both the step S2 and the step S3 are controlled to be carried out at a lower temperature, so that side reactions can be effectively inhibited, the polymerization reaction is carried out stably, and the polymer with a narrower molecular weight distribution and a more regular structure can be obtained.

In a preferred embodiment, the mass ratio of butyl acetate to mixed monomer is 1:1.

In a preferred embodiment, the catalyst is added in an amount of 2.4 to 2.6% by weight based on the total weight of the mixed monomers.

In a preferred embodiment, the distillation temperature is 240-250 ℃ and the vacuum degree is-0.085 to-0.099 MPa.

In a preferred embodiment, in the step S3, when the mixed monomer is added dropwise, the addition is stopped when the system temperature starts to rise, and the addition is continued when the system temperature rises to 50-55 ℃, and the mixed monomer is discharged after being kept at 50-55 ℃ for 1.8-2 hours.

By adopting the technical scheme, as the styrene and the myrcene react exothermically under the action of the catalyst, when the temperature of the system is raised, the reaction is initiated and carried out at an extremely high rate, if the mixed monomer is continuously dripped, the reaction temperature is higher, the danger coefficient of the whole reaction process is increased, side reactions are increased at high temperature, the chain transfer and chain termination rates are different, the molecular weight of the generated polymer is uneven, the product structure is uncontrollable, if the excessive temperature can cause the myrcene to generate excessive crosslinking, the softening point of the final polymer is reduced, and when the temperature of the system is kept within the range of 50-55 ℃, the stable and controllable polymerization of the mixed monomer can be realized, thereby being beneficial to forming the polymer with a more regular structure and high softening point.

In a preferred embodiment, in the step S4, the polymerization solution is washed with hot water at 95 to 100 ℃.

By adopting the technical scheme, the catalyst and impurities in the polymerization liquid can be effectively removed when the hot water with the temperature of 95-100 ℃ is used for washing for multiple times, so that the purity of the terpene styrene resin is ensured.

In a preferred embodiment, the water content of the mixed monomers is controlled to be 300ppm or less after the mixed monomers are stirred and mixed.

In a preferred embodiment, the catalyst is aluminum trichloride.

In a second aspect, the present invention provides a terpene styrene resin obtained by the method for preparing a terpene styrene resin with a high softening point, wherein the softening point of the terpene styrene resin is more than or equal to 130 ℃.

In summary, the invention has the following beneficial effects:

In addition, the use amount of the styrene monomer is between 30 and 40 percent, the recognition that the softening point of the terpene styrene resin is greatly reduced when the content of the existing styrene monomer is more than 15 percent is broken, and the addition of a large amount of styrene monomer not only reduces the use amount of the myrcene monomer and reduces the preparation cost, but also ensures the low polarity of the terpene styrene resin when the content of the styrene is more than 30 percent, so that the hot melt adhesive prepared from the terpene styrene resin with high softening point generates higher adhesive force to polar substrates such as PC, glass, metal, rubber tires and the like, and has higher application value.

Drawings

FIG. 1 is a molecular weight measurement report screenshot of terpene styrene resin of example 1 of the present application.

FIG. 2 is an infrared spectrum of the molecular structure of the terpene styrene resin of example 1 of the present application.

FIG. 3 is a molecular weight measurement report screenshot of the terpene styrene resin of comparative example 1 of the present application.

FIG. 4 is a molecular weight measurement report screenshot of the terpene styrene resin of comparative example 2 of the present application.

FIG. 5 is a molecular weight measurement report screenshot of the terpene styrene resin of comparative example 3 of the present application.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings. All reagents were not manufacturer-identified and were conventional reagent products commercially available.

In the prior art, terpene styrene resin is prepared by copolymerizing 85% of turpentine (the main components are alpha-pinene and beta-pinene) and 15% of styrene under toluene solvent to obtain resin with a softening point of 100-115 ℃, and the softening point is reduced along with the increase of the styrene content, wherein the softening point is reduced because the crosslinking effect among resin molecules is weakened along with the increase of the styrene content, so that a three-dimensional network structure is loose, the molecular chain movement resistance is reduced, and the softening point is reduced along with the reduction.

Example 1

s1, calculating according to the proportion of styrene of 30wt% and the proportion of myrcene of 70%, stirring and mixing 1650g of styrene and 3850g of myrcene for 30 minutes, standing for 30 minutes, and then separating water to clean to obtain a mixed monomer with the water content of 300ppm, wherein the myrcene adopts turpentine myrcene;

s2, adding 5500g of anhydrous butyl acetate into a polymerization kettle, stirring, adding 132g of catalyst aluminum trichloride when the temperature in the kettle is reduced to 15 ℃, and continuously stirring and mixing, wherein the addition amount of the catalyst is 2.4% of the total amount of the mixed monomers;

S3, dropping the mixed monomer when the temperature in the kettle in the step S2 is reduced to 10 ℃, stopping dropping when the temperature of the system begins to rise to 22 ℃, continuing dropping when the temperature of the system rises to 50 ℃ until the mixed monomer is completely dropped, preserving heat for 2 hours at 50 ℃ and discharging to obtain a polymerization solution, wherein the yield of the polymerization solution is 92%;

S4, placing the polymerization solution in hot water at 95 ℃ for washing to be neutral, standing for 30 minutes, discharging the water in the polymerization solution, adding the polymerization solution into a distillation kettle for distillation to remove the solvent, distilling at 240 ℃ and the vacuum degree of-0.085 MPa, discharging after 30 minutes of distillation, and granulating to obtain the terpene styrene resin with high softening point.

Example 2

The difference from example 1 is that the parameters are varied, as follows

S1, mixing 1925g of styrene and 3575g of myrcene for 30 minutes under stirring according to the proportion of 35wt% of styrene and 65% of myrcene, and standing for 30 minutes, and then separating water to clean to obtain a mixed monomer with the water content of 300ppm, wherein the myrcene adopts turpentine myrcene;

s2, adding 5500g of anhydrous butyl acetate into a polymerization kettle, stirring, adding 137.5g of catalyst aluminum trichloride when the temperature in the kettle is reduced to 15 ℃, and continuously stirring and mixing, wherein the adding amount of the catalyst is 2.5% of the total amount of the mixed monomers;

s3, dropping the mixed monomer when the temperature in the kettle in the step S2 is reduced to 10 ℃, stopping dropping when the temperature of the system begins to rise to 21 ℃, continuing dropping when the temperature of the system rises to 55 ℃ until the mixed monomer is completely dropped, preserving heat for 1.8 hours at 55 ℃ and discharging to obtain a polymerization solution, wherein the yield of the polymerization solution is 91%;

S4, placing the polymerization solution in hot water at 100 ℃ for water washing to be neutral, standing for 30 minutes, discharging the water in the polymerization solution, adding the polymerization solution into a distillation kettle for distillation to remove the solvent, distilling at 250 ℃ and the vacuum degree of-0.099 MPa, discharging after 30 minutes of distillation, and granulating to obtain the terpene styrene resin with high softening point.

Example 3

The difference from example 1 is that the parameters are varied, as follows

S1, calculating according to the proportion of styrene 40wt% and the proportion of myrcene 60%, stirring and mixing 2200g of styrene and 3300g of myrcene for 30 minutes, standing for 30 minutes, and then separating water to clean to obtain a mixed monomer with the water content of 300ppm, wherein the myrcene adopts turpentine myrcene;

S2, adding 5500g of anhydrous butyl acetate into a polymerization kettle, stirring, adding 143g of catalyst aluminum trichloride when the temperature in the kettle is reduced to 15 ℃, and continuously stirring and mixing, wherein the adding amount of the catalyst is 2.6% of the total amount of the mixed monomers;

s3, dropping the mixed monomer when the temperature in the kettle in the step S2 is reduced to 10 ℃, stopping dropping when the temperature of the system begins to rise to 22 ℃, continuing dropping when the temperature of the system rises to 55 ℃ until the mixed monomer is completely dropped, preserving heat for 2 hours at 55 ℃ and discharging to obtain a polymerization solution, wherein the yield of the polymerization solution is 91%;

Comparative example 1

A preparation method of terpene styrene resin, wherein the styrene content is 30wt% and the myrcene content is 70%, is different from example 1 in that toluene is used instead of butyl acetate in the same amount, and the other is the same as example 1.

Comparative example 2

A preparation method of terpene-styrene resin was different from example 1 in that the total amount of the mixed monomers was 5500g, the styrene content was 50wt% and the myrcene content was 50wt%, which were the same as in example 1.

Comparative example 3

A preparation method of terpene styrene resin was different from example 1 in that the total amount of the mixed monomers was 5500g, the styrene content was 40wt% and the myrcene content was 60wt%, and the butyl acetate was replaced with an equal amount of toluene, all of which were the same as in example 1.

Performance detection

1. The terpene styrene resins obtained in the above examples and comparative examples were subjected to the softening point test, and the softening point test was conducted with reference to the relevant regulations in GB 12007.6-89 "method for measuring softening point of epoxy resin-ring and ball method", and the test results are shown in Table 1.

2. The number average molecular weight of the terpene styrene resin obtained in example 1 was measured by chromatography, the measurement results are shown in FIG. 1, the molecular weight measurement results of the terpene styrene resin obtained in other examples are substantially similar to those of example 1, and the drawings will not be repeated, and the number average molecular weight measurement graphs of comparative examples 1 to 3 are shown in FIGS. 3 to 5.

3. The molecular structure and chemical bond of the terpene styrene resin obtained in example 1 were examined, and the results of the examination are shown in FIG. 2. The molecular structure of the terpene styrene resin obtained in other examples is substantially the same as that in example 1, and the drawings will not be repeated.

TABLE 1 results of terpene styrene resin Performance test

Project	Softening point °c	Number average molecular weight
Project	Softening point °c	Number average molecular weight	Example 1	135	1000
Example 2	132	986	Example 1	135	1000
Example 2	132	986	Example 3	130	968
Comparative example 1	115	835	Example 3	130	968
Comparative example 1	115	835	Comparative example 2	90	691
Comparative example 3	100	796	Comparative example 2	90	691

In connection with the test data of table 1:

According to the application, the softening point of the terpene styrene resin obtained by the method can reach 130 ℃ by regulating and controlling the selection of styrene, myrcene and solvent, and the technical bottleneck of low softening point of the conventional terpene styrene resin with increased styrene content is broken through.

Comparative example 1 compared with example 1, when styrene and myrcene were used in the same ratio as in example 1, the terpene styrene resin obtained in comparative example 1 had a softening point of 115℃after butyl acetate was replaced with toluene, the softening point was greatly reduced compared with example 1, and as can be seen from FIG. 3, the value of the Z-average molecular weight was greatly reduced compared with that in FIG. 1, indicating that the molecular weight of the high molecular chain of the terpene styrene resin obtained in comparative example 1 was reduced, which may be due to the fact that the chain transfer property of toluene was inferior to that of butyl acetate, and therefore when toluene was used as the solvent, a terpene styrene resin having a higher molecular weight could not be obtained, and the softening point was reduced.

Comparative example 2 when the contents of styrene and myrcene were 50% as compared with example 1, the terpene styrene resin obtained in comparative example 2 had a softening point of 90C and its molecular weight was also significantly reduced, indicating that the addition of excess styrene significantly reduced the softening point of the terpene styrene resin.

Comparative example 3 the terpene styrene resin obtained in comparative example 3 had a softening point of 100C, which was much lower than that in example 1, when the styrene content was 40% and the myrcene content was 60% as compared with example 1, and toluene was used in place of butyl acetate at the same time, and it was further demonstrated that the blending of styrene, myrcene and butyl acetate effectively improved the softening point of the terpene styrene resin.

4. Sanitary adhesive tape performance detection:

25g of terpene styrene resin obtained in the above example or comparative example, 15g of SBS and 10g of naphthenic oil are added into 100g of toluene, mixed uniformly, reacted for 12 hours at room temperature, then coated on a base material, the coating thickness is 200 mu m, vacuum dried under 130 ℃ to obtain a sanitary adhesive tape, and the annular initial adhesion test, 24h peeling test and holding viscosity performance test are carried out, wherein the test results are shown in Table 2, and the specific tests are as follows:

Annular Primary tack test the test is carried out with reference to the relevant regulations in GB/T31125-2014 annular method for adhesive tape Primary tack test method.

24H peel test-test by referring to GB/T2792-2014 test method for adhesive tape peel strength, average peel force and peel strength are recorded.

The adhesive holding performance is detected by referring to a method A in GB/T4851-2014 adhesive tape adhesive holding test method, wherein the adhesive holding detection condition is that one end of an adhesive tape is adhered in a 25 mm-25 mm area range of a stainless steel sample plate, and a weight with the weight of 1kg is hung at the lower end, and the experiment temperature is 40 ℃.

TABLE 2 results of terpene styrene resin Performance test

Continuous table 2

In connection with the test data of table 2:

The terpene styrene resin obtained in the embodiments 1-3 of the application has good primary adhesion and lasting adhesion capability to stainless steel and plastics, and the peeling force at 20min is basically the same as the peeling force at 24h, which further indicates that the adhesive obtained by using the terpene styrene resin has good primary adhesion performance.

Comparative examples 1-3 the adhesion properties of terpene styrene resins having softening points of 90-115C to stainless steel and plastics were greatly reduced compared to the high softening point terpene styrene resin obtained in example 1 of the present application, further demonstrating that the high softening point terpene styrene resins of the present application have good adhesion ability.

The embodiments of the present invention are all preferred embodiments of the present invention, and are not limited in scope by the present invention, so that all equivalent changes according to the structure, shape and principle of the present invention are covered by the scope of the present invention.

Claims

1. A method for preparing a high softening point terpene styrene resin, characterized by comprising the following steps:

S1. Styrene and myrcene are mixed to obtain a mixed monomer, wherein the amount of styrene is 30-40% and the amount of myrcene is 60-70% by weight percentage;

S2. The butyl acetate and the catalyst are mixed evenly at a temperature ≤15℃, wherein the mass ratio of the butyl acetate to the mixed monomers is 1:1.

S3. When the temperature of the system in step S2 is ≤10℃, add the mixed monomer dropwise. When adding the mixed monomer, stop adding when the system temperature starts to rise. When the system temperature rises to 50-55℃, continue adding. After keeping the temperature at 50-55℃ for 1.8-2 hours, discharge the material to obtain the polymerization liquid.

S4. The polymerization solution is washed with hot water until neutral and then distilled to obtain a high softening point terpene styrene resin.

2. The method for preparing a high softening point terpene styrene resin according to claim 1, characterized in that: the amount of catalyst added is 2.4-2.6% of the total weight of the mixed monomers.

3. The method for preparing a high softening point terpene styrene resin according to claim 1, characterized in that: the distillation temperature is 240-250℃ and the vacuum degree is -0.085~-0.099MPa.

4. The method for preparing a high softening point terpene styrene resin according to claim 1, characterized in that: in step S4, the polymerization solution is washed with hot water at 95-100℃.

5. The method for preparing a high softening point terpene styrene resin according to claim 1, characterized in that: the moisture content is controlled to be below 300 ppm after the mixed monomers are stirred and mixed.

6. The method for preparing a high softening point terpene styrene resin according to claim 1, wherein the catalyst is aluminum trichloride.

7. A terpene styrene resin obtained by the preparation method of the high softening point terpene styrene resin according to any one of claims 1-6, characterized in that: the softening point of the terpene styrene resin is ≥130℃.